CN108333876B - Photosensitive film laminate and cured product formed using same - Google Patents

Photosensitive film laminate and cured product formed using same Download PDF

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Publication number
CN108333876B
CN108333876B CN201810034826.8A CN201810034826A CN108333876B CN 108333876 B CN108333876 B CN 108333876B CN 201810034826 A CN201810034826 A CN 201810034826A CN 108333876 B CN108333876 B CN 108333876B
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photosensitive
resin
photosensitive film
group
film
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CN108333876A (en
Inventor
舟越千弘
冈田和也
北村太郎
佐藤和也
荒井康昭
伊藤信人
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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Priority claimed from JP2017032612A external-priority patent/JP6215497B1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is a photosensitive film laminate which can suppress the influence on the photosensitive film surface even when strong impact or pressing is applied when a substrate or the like on which the photosensitive film laminate is laminated is superposed. A photosensitive film laminate comprising, in order, a support film, an intermediate layer, and a photosensitive film formed from a photosensitive resin composition, wherein the intermediate layer comprises at least one of melamine and a melamine compound.

Description

Photosensitive film laminate and cured product formed using same
Technical Field
The present invention relates to a photosensitive film laminate and a cured product formed using the same.
Background
In general, in a printed circuit board used in an electronic device or the like, a solder resist layer is formed on a region other than a connection hole on a substrate on which a circuit pattern is formed in order to prevent solder from adhering to an unnecessary portion when an electronic component is mounted on the printed circuit board.
With recent trend toward higher precision and higher density of printed circuit boards due to miniaturization of electronic devices, it is becoming mainstream to form a solder resist layer using a so-called photosensitive solder resist, that is, to apply a photosensitive resin composition to a substrate, dry the composition, form a pattern by exposure and development, and then to cure the patterned resin formally by heating or irradiation with light.
In addition, the following schemes are also proposed: the solder resist layer is formed using a so-called photosensitive film laminate having a photosensitive film, without using the liquid photosensitive resin composition. Such a photosensitive film laminate is generally formed by laminating a photosensitive film formed of a photosensitive resin composition on a support film, and if necessary, a protective film may be laminated on the surface of the photosensitive film. When such a photosensitive film laminate is used, the protective film is peeled off and laminated on the wiring board by thermocompression bonding, and the support film is peeled off and developed before exposure or after exposure from the support film side, whereby a patterned solder resist layer can be formed. By using the photosensitive film laminate, a drying step after coating can be omitted, and the obtained solder resist layer is excellent in surface smoothness and surface hardness as compared with the case of wet coating. Further, in recent years, there is a tendency to thin a photosensitive film from the viewpoint of workability, and not only the photosensitive film but also a support film in which the photosensitive film is laminated has a tendency to thin (for example, refer to international publication No. 2010/013charge 23, japanese patent application laid-open No. 2011-48270, and the like).
Disclosure of Invention
In the step of forming the solder resist layer on the wiring board as described above, the laminated wiring board may be temporarily stored while being sequentially stacked in a period from the time when the photosensitive film laminate is laminated on the wiring board to the time when the photosensitive film laminate is advanced to the time before the next step. In this case, the surface of the photosensitive film laminate provided on the wiring board may be damaged due to an impact when the wiring boards to which the photosensitive film laminate is attached are stacked or a self weight when the wiring boards are stacked. In particular, due to the recent influence of the thinning of the photosensitive film laminate, not only the support film but also the photosensitive film surface laminated on the support film may be damaged due to the impact at the time of lamination or the pressing by its own weight.
Accordingly, an object of the present invention is to provide a photosensitive film laminate capable of suppressing an influence on a photosensitive film surface even when strong impact or pressing is applied when a substrate or the like on which the photosensitive film laminate is laminated is superposed. Another object of the present invention is to provide a cured product formed using the photosensitive film laminate.
The present inventors have found that, at this time, damage to the photosensitive film surface due to impact or pressing when the substrate or the like on which the photosensitive film laminate is laminated is caused not only by the impact resistance of the photosensitive film itself but also by the material of the layer in contact with the photosensitive film surface, that is, the layer in direct contact with the photosensitive film. Further, the present inventors have found that, by forming a laminate in which an intermediate layer containing a specific component is provided between a support film and a photosensitive film, even when a substrate or the like on which the photosensitive film laminate is laminated is subjected to lamination, strong impact or pressing can be suppressed from affecting the surface of the photosensitive film. Further, the present inventors have found that the solder resist layer formed using the photosensitive film laminate having the intermediate layer containing the above specific component does not affect the surface thereof by impact, and thus can improve the yield. The present invention has been made based on the above-described technical ideas.
[1] The photosensitive film laminate according to embodiment 1 of the present invention is a photosensitive film laminate comprising, in order, a support film, an intermediate layer, and a photosensitive film formed from a photosensitive resin composition,
the intermediate layer is formed by containing at least one of melamine and a melamine compound.
[2] The photosensitive film laminate according to embodiment 2 of the present invention is the photosensitive film laminate according to [1], wherein the support film has a thickness of 10 μm to 150 μm.
[3] The photosensitive film laminate according to embodiment 3 of the present invention is the photosensitive film laminate according to claim 1 or 2, wherein the photosensitive resin composition contains a filler and a crosslinking component.
[4] The photosensitive film laminate according to embodiment 4 of the present invention is the photosensitive film laminate according to any one of [1] to [3], wherein the photosensitive film laminate further comprises a protective film on a surface side of the photosensitive film opposite to the intermediate layer.
[5] A cured product according to embodiment 5 of the present invention is formed using the photosensitive film laminate according to any one of [1] to [4 ].
According to the present invention, by forming the photosensitive film laminate in which the intermediate layer containing the above specific component is provided between the photosensitive film and the support film, even when the substrate or the like on which the photosensitive film laminate is laminated is superimposed by strong impact or pressing, the influence on the surface of the photosensitive film can be suppressed. In particular, the photosensitive film laminate is effective when used for forming a solder resist layer. In addition, the above-described effect can be exhibited even if the support film is a thin film, and this is effective from the viewpoint. In addition, according to another aspect of the present invention, a cured product formed using the photosensitive film laminate can be realized.
Drawings
Fig. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive film laminate of the present invention.
Fig. 2 is a schematic cross-sectional view showing another embodiment of the photosensitive film laminate of the present invention.
Detailed Description
The photosensitive film laminate of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive film laminate of the present invention. The photosensitive film laminate 1 of the present invention has a structure in which a support film 10, an intermediate layer 20, and a photosensitive film 30 formed of a photosensitive resin composition are laminated in this order. Here, the photosensitive film is a film-like photosensitive resin composition, and is a film-like photosensitive resin composition in which other layers such as a support film and a protective film are not laminated. In addition, the present invention may be provided with other films or the like in addition to the above-described configuration. For example, in consideration of the handleability of the photosensitive film laminate while preventing dust or the like from adhering to the surface of the photosensitive film, as shown in fig. 2, a protective film 40 may be further provided on the photosensitive film laminate 1 on the side opposite to the intermediate layer 20 of the photosensitive film 30. The following describes each constituent element constituting the film laminate of the present invention.
[ support film ]
The support film in the photosensitive film laminate of the present invention has the following functions: the photosensitive film described later is supported, and a predetermined surface morphology is imparted to the surface of the photosensitive film on the side in contact with the support film at the time of exposure and development of the photosensitive film as described later.
The support film in the photosensitive film laminate of the present invention is not particularly limited as long as it is a known support film, and for example, a film made of a thermoplastic resin such as a polyester film, a polyimide film, a polyamide-imide film, a polypropylene film, or a polystyrene film of polyethylene terephthalate, polyethylene naphthalate, or the like can be suitably used. In the case of using the thermoplastic resin film, a filler (mixing treatment) may be added to the resin at the time of film formation, matting coating treatment (coating treatment) may be performed, and a spray treatment such as sand blast treatment may be performed on the film surface, or a hairline treatment, chemical etching, or the like may be performed. Among these, polyester films can be suitably used in terms of heat resistance, mechanical strength, handleability, and the like. The support film may be a single layer or may be laminated with 2 or more layers.
For the purpose of improving the strength, it is preferable to use a film stretched in a uniaxial direction or a biaxial direction.
From the viewpoint of handleability, the thickness of the support film is preferably in the range of 10 to 150 μm, more preferably in the range of 10 to 100 μm, and even more preferably in the range of 10 to 50 μm.
In addition, a structure in which a support film having an intermediate layer described later provided on the support film by coating is integrated with the intermediate layer may be used.
< intermediate layer >
The intermediate layer in the photosensitive film laminate of the present invention contains at least one of melamine and a melamine compound. The present inventors have conducted intensive studies and as a result, have found that the surface of a photosensitive film is not affected by a strong impact by providing an intermediate layer made of a specific material between a support film and the photosensitive film. The reason for this is not necessarily clear, but it is assumed that the intermediate layer protects the surface of the laminated photosensitive film from a strong impact, and as a result, the surface state of the photosensitive film is not affected, but this is merely an assumed range and is not necessarily limited thereto.
From the viewpoint of protecting the photosensitive film, the thickness of the intermediate layer is preferably in the range of 0.1 to 10 μm, more preferably in the range of 1 to 8 μm.
The melamine and the melamine compound contained in the intermediate layer may be any known and used ones. In addition, in the present invention, the melamine compound also includes a mixture of the melamine compound and other substances. In the present invention, "melamine" means a resin cured by addition condensation of melamine (2, 4, 6-triamino-1, 3, 5-triazine) with formaldehyde, and the concept of the resin also includes methylolmelamine as an initial reactant of the melamine and formaldehyde and alkylated methylolmelamine as an alkylate thereof. The melamine may also include modified melamine such as methylated methylolmelamine, propylated methylolmelamine, butylated methylolmelamine, and isobutylated methylolmelamine. In addition, melamine modified products such as melamine (meth) acrylate are included.
The melamine compound is a mixture of the melamine and other resins such as acrylic resin, epoxy resin, and alkyd resin, and examples thereof include acrylic melamine, alkyd melamine, polyester melamine, and epoxy melamine. Among these, melamine acrylate and melamine epoxy are preferable, and melamine acrylate is more preferable, because more excellent impact resistance can be obtained. Here, the term "melamine acrylate" refers to a mixture of an acrylic resin and a melamine resin, and refers to a type in which the acrylic resin is cured with the melamine resin. In addition, epoxy melamine refers to a mixture of an epoxy resin and a melamine resin, and refers to a type in which an epoxy resin is cured with a melamine resin. Specific examples of melamine include AMIDIR J-820-60, L-109-65, L-117-60, L-127-60, 13-548, G-821-60, L-110-60G, L-125-60, L-166-60B, L-105-60 manufactured by DIC, U-VAN 20SE60, 20SB, 22R, 125, 132, 62, 60R, 169 manufactured by Mitsui chemical Co., ltd. The acrylic resin and the epoxy resin may be any known and used ones without particular limitation. Specific examples of the acrylic resin include ACRYDIC 54-172-60, A-322, A-405, A-452, etc. manufactured by DIC Co., ltd. Further, specific examples of the epoxy resin include eponik R301 manufactured by mitsubishi chemical corporation. The content of the melamine resin is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, relative to the total amount with the acrylic resin or the epoxy resin.
The mixing amount of melamine and the melamine compound contained in such an intermediate layer is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, with respect to the entire layer.
The intermediate layer may contain other resins within the range of no loss of effect. In particular, it is preferable that the intermediate layer contains a silicone resin as a resin component. In the photosensitive film laminate of the present invention, when the photosensitive film is cured to form a cured film, the support film and the intermediate layer need to be peeled off from the photosensitive film (cured film), and the silicone resin is contained in the intermediate layer, so that the support film and the intermediate layer can be easily peeled off from the photosensitive film, and the adhesion between the support film and the intermediate layer can be maintained. Further, by including the melamine or the melamine compound and the silicone resin in the intermediate layer, damage to the surface of the photosensitive film due to impact or extrusion can be further suppressed. The silicone resin may be used without particular limitation, and examples thereof include SYMAC US-120, US-150, US-270, US-350, aron GS-30, and the like manufactured by Toyaku Kagaku Co.
The intermediate layer may contain a filler, a curing accelerator, an additive, an antistatic agent, or the like as a component other than the resin. The filler is not particularly limited, and known fillers may be used, and examples thereof include silica and calcium carbonate. Among these, silica is preferable. The average particle diameter of the filler is not particularly limited, but is preferably 1.0 to 5.5. Mu.m, more preferably 2.0 to 4.5. Mu.m, and still more preferably 2.0 to 3.0. Mu.m. Among these, cationic surfactants containing quaternary ammonium salts represented by the following general formula (I) as a main component can be suitably used. The intermediate layer contains a cationic surfactant represented by the following formula, whereby damage to the surface of the photosensitive film due to impact or extrusion can be further suppressed.
(wherein R represents an alkyl group having 8 or more carbon atoms, R 1 Represents lower alkyl, R 2 Represents a lower alkylene group. )
Among the cationic surfactants of the above formula (I), those represented by the following general formula (II) can be more preferably used.
(wherein R represents an alkyl group having 8 or more carbon atoms.)
< photosensitive film >
The photosensitive film constituting the photosensitive film laminate of the present invention is patterned by exposure and development to form a cured coating film provided on a circuit substrate. As the cured coating film, a solder resist layer is preferable. Such a photosensitive film can be formed using a photosensitive resin composition, and a conventionally known solder resist ink or the like can be used without limitation, and an example of a photosensitive resin composition that can be preferably used in the photosensitive film of the present invention will be described below.
In the present invention, the photosensitive resin composition preferably contains a crosslinking component and a filler. Further, it is more preferable to include a photopolymerization initiator. The crosslinking component is preferably a carboxyl group-containing photosensitive resin or a photosensitive monomer, and when further heated, it preferably contains a component that is crosslinked by heat. The following describes the respective components.
[ crosslinking component ]
The crosslinking component is not particularly limited as long as it is a component that performs crosslinking, and a known and conventional crosslinking component can be used. Particularly, the carboxyl group-containing photosensitive resin or the photosensitive monomer is preferable, and in the case of further heating, a component crosslinked by heat (hereinafter referred to as a thermal crosslinking component) is preferably contained.
The carboxyl group-containing photosensitive resin is a component that is polymerized or crosslinked by light irradiation to be cured, and can be made alkali developable by containing a carboxyl group. In addition, from the viewpoints of photocurability and development resistance, it is preferable that the resin composition has an ethylenically unsaturated bond in the molecule in addition to a carboxyl group. As ethylenically unsaturated double bonds, preference is given to those derived from acrylic acid or methacrylic acid or derivatives thereof.
As the carboxyl group-containing photosensitive resin, a carboxyl group-containing photosensitive resin which does not use an epoxy resin as a starting material is preferably used. The carboxyl group-containing photosensitive resin, which does not use an epoxy resin as a starting material, has a very small halide ion content, and deterioration of insulation reliability can be suppressed. Specific examples of the carboxyl group-containing photosensitive resin include the compounds listed below (which may be either oligomers or polymers).
Examples of the method include:
(1) A carboxyl group-containing photosensitive resin obtained by reacting a 2-functional or more polyfunctional (solid) epoxy resin with (meth) acrylic acid, and adding a 2-membered acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or the like to a hydroxyl group present in a side chain;
(2) Further epoxidizing the hydroxyl groups of the 2-functional (solid) epoxy resin with epichlorohydrin, reacting the obtained multifunctional epoxy resin with (meth) acrylic acid, and adding 2-membered acid anhydride to the generated hydroxyl groups to obtain a carboxyl group-containing photosensitive resin;
(3) A carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having 2 or more epoxy groups in 1 molecule with a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic acid with the alcoholic hydroxyl group of the obtained reaction product;
(4) A carboxyl group-containing photosensitive resin obtained by reacting a compound having 2 or more phenolic hydroxyl groups in 1 molecule, such as bisphenol a, bisphenol F, bisphenol S, novolak type phenol resin, a condensate of poly-p-hydroxystyrene, naphthol and aldehydes, a condensate of dihydroxynaphthalene and aldehydes, with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the obtained reaction product with a polybasic acid anhydride;
(5) A carboxyl group-containing photosensitive resin obtained by reacting a compound having 2 or more phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride;
(6) A carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal end of a urethane resin obtained by polyaddition reaction of an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, a diisocyanate compound such as an aromatic diisocyanate, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a-based epoxy alkane adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group;
(7) In the synthesis of a carboxyl group-containing urethane resin by addition polymerization of a carboxyl group-containing diol compound such as diisocyanate, dimethylolpropionic acid, dimethylolbutyric acid, etc., and a diol compound, a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule such as hydroxyalkyl (meth) acrylate is added, whereby a carboxyl group-containing urethane resin having (meth) acrylated at the end thereof;
(8) In the synthesis of a carboxyl group-containing urethane resin by the addition polymerization reaction of a diisocyanate, a carboxyl group-containing diol compound, and a diol compound, a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, is added to thereby give a carboxyl group-containing urethane resin having a terminal (meth) acrylated;
(9) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., adding 2-membered acid anhydride to the primary hydroxyl group formed, and further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule such as glycidyl (meth) acrylate and α -methyl glycidyl (meth) acrylate to the carboxyl group-containing polyester resin obtained;
(10) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in 1 molecule to any of the carboxyl group-containing photosensitive resins of (1) to (9) above;
(11) Carboxyl group-containing photosensitive resins obtained by reacting a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, such as 3, 4-epoxycyclohexylmethacrylate, with a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, isobutylene, or the like; etc. Here, (meth) acrylate is a term generically used for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.
Among the carboxyl group-containing photosensitive resins, as described above, carboxyl group-containing photosensitive resins obtained by synthesizing resins other than epoxy resins without using epoxy resins as starting materials can be suitably used. Therefore, in the specific examples of the carboxyl group-containing photosensitive resin, any one or more of the carboxyl group-containing photosensitive resins (4) to (8) and (11) can be suitably used, and in particular, the resins exemplified in (4) to (8) can be suitably used. Can have the characteristics required for the solder resist for semiconductor packaging, namely PCT resistance, HAST resistance and cold and hot shock resistance.
Thus, by not using an epoxy resin as a starting material, the amount of chlorine ion impurities can be suppressed to a very small amount of, for example, 100ppm or less. The content of chloride ion impurities in the carboxyl group-containing photosensitive resin suitably used in the present invention is 0 to 100ppm, more preferably 0 to 50ppm, still more preferably 0 to 30ppm.
In addition, by not using an epoxy resin as a starting material, a resin containing no hydroxyl group (or having a reduced amount of hydroxyl groups) can be easily obtained. In general, the presence of hydroxyl groups is known to have excellent characteristics such as improved adhesion due to hydrogen bonding, but moisture resistance is significantly reduced, and moisture resistance can be improved by forming a carboxyl group-containing photosensitive resin containing no hydroxyl groups.
It is also preferable to use a carboxyl group-containing urethane resin synthesized from an isocyanate compound which does not use phosgene as a starting material and a starting material which does not use epihalohydrin, and having a chlorine ion impurity amount of 0 to 30 ppm. In such a urethane resin, by matching the equivalent weights of the hydroxyl group and the isocyanate group, a resin containing no hydroxyl group can be easily synthesized.
In addition, in the synthesis of the urethane resin, an epoxy acrylate-modified raw material may be used as the diol compound. The chlorine ion impurities may enter, and may be used in view of the capability of controlling the amount of chlorine ion impurities.
The carboxyl group-containing photosensitive resin has a large number of carboxyl groups in the side chain of the polymer main chain, and thus can be developed with an alkaline aqueous solution.
The acid value of the carboxyl group-containing photosensitive resin is preferably 40 to 150mgKOH/g. The acid value of the carboxyl group-containing photosensitive resin is set to 40mgKOH/g or more, whereby alkali development is improved. In addition, by setting the acid value to 150mgKOH/g or less, a normal resist pattern can be easily drawn. More preferably 50 to 130mgKOH/g.
The weight average molecular weight of the carboxyl group-containing photosensitive resin varies depending on the resin skeleton, and is generally preferably 2,000 ～ 150,000. By setting the weight average molecular weight to 2,000 or more, the non-tackiness and resolution can be improved. In addition, by setting the weight average molecular weight to 150,000 or less, developability and storage stability can be improved. More preferably 5,000 ～ 100,000.
The mixing amount of the carboxyl group-containing photosensitive resin is preferably 20 to 60% by mass in terms of solid content in the entire composition. By being 20 mass% or more, the coating film strength can be improved. In addition, when the content is 60 mass% or less, the tackiness becomes appropriate, and the workability improves. More preferably 30 to 50 mass%.
Examples of the compound used as the photosensitive monomer include known and used polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. Specifically, it is possible to select from: hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N-dimethylaminopropyl acrylamide, and the like; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol and trihydroxyethyl isocyanurate, and polyhydric acrylic esters such as an ethylene oxide adduct, propylene oxide adduct and epsilon-caprolactone adduct thereof; a phenoxy acrylate, bisphenol a diacrylate, and a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct of these phenols; polyglycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; not limited to the above, any one of at least one of acrylic esters and melamine acrylic esters obtained by directly acrylating a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol, or by urethane acrylating a diisocyanate, and methacrylic esters corresponding to the above acrylic esters is suitably selected and used.
An epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid; further, an epoxy urethane acrylate compound obtained by reacting a hydroxyl acrylate such as pentaerythritol triacrylate with a half urethane compound of a diisocyanate such as isophorone diisocyanate with respect to the hydroxyl group of the epoxy acrylate resin is used as a photosensitive monomer. Such an epoxy acrylate resin can improve photocurability without reducing touch dryness.
When the carboxyl group-containing resin is contained in the composition, the mixing amount of the compound having an ethylenically unsaturated group in the molecule used as the photosensitive monomer is preferably 5 to 100 parts by mass, more preferably 5 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing resin in terms of solid content. By setting the mixing amount of the compound having an ethylenically unsaturated group to 5 parts by mass or more, the photocurable property of the photocurable resin composition is improved. In addition, the coating film hardness can be improved by setting the mixing amount to 100 parts by mass or less. The carboxyl group-containing resin referred to herein includes both carboxyl group-containing photosensitive resins and carboxyl group-containing non-photosensitive resins. That is, when any of the components is blended alone in the composition, the term "alone" means alone; in the case of all mixed, this means that they are added up (the same applies in the following paragraphs).
In particular, when a carboxyl group-containing non-photosensitive resin having no ethylenically unsaturated double bond is used as the photosensitive monomer, it is effective to use a compound having 1 or more ethylenically unsaturated groups in the molecule (photosensitive monomer) for the composition to be photocurable.
Examples of the thermal crosslinking component include thermosetting resins. As the thermosetting resin, a known and used thermosetting resin such as an isocyanate compound, a blocked isocyanate compound, an amino resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, an episulfide resin, and the like can be used. Among these, preferred is a thermal crosslinking component having at least any 1 of 2 or more cyclic ether groups and cyclic thioether groups (hereinafter simply referred to as cyclic (thio) ether groups) in 1 molecule. These thermosetting components having a cyclic (thio) ether group are commercially available in various forms, and various properties can be imparted depending on the structure thereof.
The thermosetting component having 2 or more cyclic (thio) ether groups in the molecule is a compound having one or both of a plurality of cyclic ether groups having 3, 4 or 5-membered rings in the molecule, or a cyclic thioether group, and examples thereof include a compound having 2 or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound; a compound having 2 or more oxetanyl groups in the molecule, namely, a polyfunctional oxetane compound; and episulfide resins which are compounds having 2 or more sulfide groups in the molecule.
Examples of the polyfunctional epoxy compound include jor 828, jor 834, jor 1001, jor 1004, epicalon 840-S, EPICLON 850, epicalon 1050, epicalon 2055, epothoto YD 011, YD-013, YD-127, YD-128, d.e.r.317, d.e.r.331, d.e.r.661, d.e.r.664, sumieoxy ESA-011, ESA-014, ELA-115, ELA-128, a.e.r.330, a.e.r.331, a.e.r.661, a.e.r.664 (trade name) manufactured by mitsubishi chemical company; brominated epoxy resins such as joerl 903 manufactured by mitsubishi chemical Co., ltd., EPICLON 152 manufactured by DIC Co., ltd., EPICLON 165 manufactured by Santa Classification, EPOTOHOTO YDB-400 manufactured by Santa Classification Jin Zhushi, YDB-500, D.E.R.542 manufactured by Dow chemical Co., ltd., sumieoxy ESB-400 manufactured by Sumitomo chemical Co., ltd., ESB-700, A.E.R.711, A.E.R.714 manufactured by Asahi chemical Co., ltd. (trade name); jER152, jER154, d.e.n.431, d.e.n.438, epicolin N-730, epicolin N-770, epicolin-865, epoto YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104-S, RE-306, NC-3000H, sumieoxy ESCN-195-X, ESCN-220, a.e.r.ecn-235, ECN-299, etc. (all trade names) of katsuki chemical company, new japanese iron Jin Zhushi, etc. (all trade names) of the novolac epoxy resins; bisphenol F-type epoxy resins such as EPICLON 830 manufactured by DIC, jER807 manufactured by Mitsubishi chemical corporation, and EPOTOHTO YDF-170, YDF-175, and YDF-2004 manufactured by Mitsubishi Jin Zhushi, all of which are trade names; hydrogenated bisphenol A type epoxy resins such as EPOTOHOTO ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dai Jin Zhushi Co., ltd; glycidyl amine type epoxy resins such as jor 604 manufactured by mitsubishi chemical Co., ltd., epothohto YH-434 manufactured by new day iron house Jin Zhushi, sumitomo chemical industry Co., ltd., sumitomo epoxy ELM-120 (all trade names); alicyclic epoxy resins such as Celloxide 2021 (trade name) manufactured by Kagaku Kogyo Co., ltd; YL-933 manufactured by Mitsubishi chemical corporation, T.E.N., EPPN-501, EPPN-502, etc. (all trade names) of trihydroxyphenyl methane type epoxy resins; examples of such epoxy resins include a xylenol type or biphenol type epoxy resin or a mixture thereof, such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi chemical corporation; EBPS-200 manufactured by Kaiki Kagaku Co., ltd., EPX-30 manufactured by Asahi Denka Co., ltd bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by DIC Co., ltd; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by mitsubishi chemical corporation; tetrahydroxyphenylethane-type epoxy resins such as jERYL-931 (trade name) manufactured by Mitsubishi chemical corporation; TEPIC (trade name) heterocyclic epoxy resin manufactured by Nissan chemical industries Co., ltd; diglycidyl phthalate resins such as Blemmer DGT manufactured by Japanese fat & oil Co., ltd; tetraglycidyl ditolyl ethane resins such as ZX-1063 manufactured by Nippon Kagaku Jin Zhushi Co., ltd; naphthalene group-containing epoxy resins such as ESN-190, ESN-360, and HP-4032, EXA-4750, and EXA-4700 manufactured by DIC, manufactured by Nikka chemical Co., ltd; soft and tough epoxy resins having dicyclopentadiene skeleton, such as HP-7200 and HP-7200H, EXA-4816, EXA-4812 and EXA-4850, which are manufactured by DIC Co., ltd; glycidyl methacrylate copolymer epoxy resins such as CP-50S, CP-50M manufactured by Japanese fat & oil Co., ltd; and copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, etc., but are not limited thereto. These epoxy resins may be used alone or in combination of 2 or more.
Examples of the polyfunctional oxetane compound include polyfunctional oxetanes such as bis [ (3-methyl-3-oxetanylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetanylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, 3-methyl-3-oxetanylmethyl acrylate, 3-ethyl-3-oxetanylmethyl acrylate, 3-methyl-3-oxetanylmethyl methacrylate, and 3-ethyl-3-oxetanylmethyl methacrylate, and oligomers or copolymers thereof, and etherified resins such as oxetane and varnish resins, poly (p-hydroxystyrene), cardo bisphenols, calixarenes, resorcinol calixarenes (calixarenes), and semi-etherified resins having hydroxyl groups. Further, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may be mentioned.
Examples of the episulfide resin include YL7000 (bisphenol A episulfide resin) manufactured by Mitsubishi chemical corporation. Further, an episulfide resin obtained by replacing an oxygen atom of an epoxy group of a novolac-type epoxy resin with a sulfur atom by the same synthetic method may be used.
When the thermosetting component having 2 or more cyclic (thio) ether groups in the molecule is contained in the composition, the amount of the thermosetting component having 2 or more cyclic (thio) ether groups in the molecule is preferably in the range of 0.3 to 2.5 equivalents, more preferably 0.5 to 2.0 equivalents, in terms of solid content, relative to 1 equivalent of carboxyl group of the carboxyl group-containing resin. By setting the mixing amount of the thermosetting component having 2 or more cyclic (thio) ether groups in the molecule to 0.3 equivalent or more, no carboxyl groups remain in the cured coating film, and heat resistance, alkali resistance, electrical insulation, and the like are improved. In addition, the strength of the cured coating film is improved by not more than 2.5 equivalents, since the low molecular weight cyclic (thio) ether group does not remain in the dried coating film.
When a thermosetting component having 2 or more cyclic (thio) ether groups in the molecule is used, a thermosetting catalyst is preferably blended. Examples of such a heat curing catalyst include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, and hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine. Examples of the commercial products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Sikuku Kagaku Kogyo Co., ltd., U-CAT (registered trademark) 3503N, U-CAT3502T (all trade names of blocked isocyanate compounds of dimethylamine) manufactured by San-Apro Co., ltd., DBU, DBN, U-CATSA102, U-CAT5002 (all trade names of bicyclic amidine compounds and salts thereof), and the like. These are not particularly limited as long as they are a thermosetting catalyst for epoxy resins or oxetane compounds, or a material that promotes the reaction of epoxy groups and/or oxetane groups with carboxyl groups, and may be used alone or in combination of 2 or more. In addition, can also use guanamine, 2, 4-two amino-6-methyl-1, 3,5 three triazine, benzoguanamine, melamine, 2, 4-two amino-6-methyl acryloxyethyl-three triazine, 2-vinyl-2, 4-two amino-three triazine, 2-vinyl-4, 6-two amino-three triazine isocyanuric acid adduct, 2, 4-two amino-6-methyl acryloxyethyl-three triazine isocyanuric acid adduct and other three triazine derivatives, preferably used as adhesion agent and heat curing catalyst compounds.
When the thermosetting component having 2 or more cyclic (thio) ether groups in the molecule is contained in the composition, the mixing amount of the thermosetting catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the thermosetting component having 2 or more cyclic (thio) ether groups in the molecule, in terms of solid content.
The amino resin may be an amino resin such as a melamine derivative or a benzoguanamine derivative. Examples thereof include methylolmelamine compounds, methylolbenzguanamine compounds, methylolglycoluril compounds, methylol urea compounds and the like. Further, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound are obtained by converting the hydroxymethyl groups of the respective methylolmelamine compound, methylolbenzguanamine compound, methylolglycourea compound and methylol urea compound into alkoxymethyl groups. The type of the alkoxymethyl group is not particularly limited, and may be, for example, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, or the like. Particularly preferred are melamine derivatives having formaldehyde concentrations of 0.2% or less which are environmentally friendly to the human body.
As a commercially available product of the amino resin, examples thereof include Cymel 300, cymel 301, cymel 303, cymel370, cymel 325, cymel 327, cymel 701, cymel 266, cymel 267, cymel 238, cymel1141, cymel 272, cymel 202, cymel 1156, cymel 1158, cymel 1123, cymel 1170, cymel 1174, cymel UFR65, cymel 300 (manufactured by Mitsui Cyanamid, supra), NIKALAC Mx-750, NIKALAC Mx-032, NIKALAC Mx-270, NIKAC Mx-280, NIKAC Mx-290, NIKALAC Mx-706, NIKALAC Mx-708, NIKALAC Mx-40, NIKALAC Mx-31, NILAC Ms-11, NILAC Mw-30, KALAC Mw-30, NIKAMw-390, NIKAMw-NILM (manufactured by the same or the like) and NIKAMw/or the like of NIKALM-390 to NIKALM (manufactured by the same or the same).
As the isocyanate compound, a polyisocyanate compound having 2 or more isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthalene-1, 5-diisocyanate, phthalic diisocyanate, m-xylylene diisocyanate and 2, 4-benzylidene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. And adducts, biurets and isocyanurates of the isocyanate compounds listed previously.
The blocked isocyanate group contained in the blocked isocyanate compound means a group in which the isocyanate group is protected to be temporarily deactivated by reaction with a blocking agent. When heated to a predetermined temperature, the blocking agent dissociates to form isocyanate groups.
As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound capable of reacting with the blocking agent include isocyanurate type, biuret type, and addition type. Examples of the isocyanate compound used for synthesizing the blocked isocyanate compound include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include those exemplified above.
Examples of the isocyanate blocking agent include phenol blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based end-capping agents such as epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam and beta-propiolactam; active methylene-based blocking agents such as ethyl acetoacetate and acetylacetone; alcohol-based capping agents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate, and ethyl lactate; oxime-based end-capping agents such as aldoxime, acetoxime, methylethylketoxime, diacetyl monoxime, and cyclohexanoxime; thiol-based end capping agents such as butanethiol, hexanethiol, t-butylmercaptan, thiophenol, methyl thiophenol, ethyl thiophenol and the like; amide-based end capping agents such as acetamides and benzamides; imide-based end capping agents such as succinimide and maleimide; amine-based end capping agents such as dimethylaniline, aniline, butylamine, dibutylamine and the like; imidazole-based end capping agents such as imidazole and 2-ethylimidazole; imine-based end-capping agents such as methylene imine and propylene imine.
Examples of the blocked isocyanate compound include Sumidur BL-3175, BL-4165, BL-1100, BL-1265, desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, desmotherm 2170, desmotherm 2265 (manufactured by Sumika Bayer Urethane Co., ltd., trade name), CORONATE 2512, CORONATE 2513, CORONATE 2520 (manufactured by Tosoh Co., trade name), B-830, B-815, B-846, B-870, B-874, B-882 (manufactured by Mitsui TakedaChemicals Co., trade name), TPA-B80E, 17B-60, and E402-B80T (manufactured by Asahi chemical Co., ltd., trade name). Sumidur BL-3175 and BL-4265 were obtained using methylethyl oxime as a blocking agent.
In the photosensitive resin composition, a urethane catalyst may be blended in order to promote the curing reaction of the hydroxyl group, the carboxyl group and the isocyanate group. As the urethanization catalyst, it is preferable to use at least any one kind of urethanization catalyst selected from tin-based catalysts, metal chlorides, metal acetylacetonates, metal sulfates, amine compounds, and amine salts.
Examples of the tin catalyst include organotin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds. Examples of the metal chloride include chlorides of metals selected from the group consisting of Cr, mn, co, ni, fe, cu and Al, for example, cobalt perchlorate, nickel dichloride, and ferric chloride. Examples of the metal acetylacetonate include acetylacetonates of metals selected from the group consisting of Cr, mn, co, ni, fe, cu and Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, and the like. Further, as the metal sulfate, there may be mentioned a sulfate of a metal selected from the group consisting of Cr, mn, co, ni, fe, cu and Al, for example, copper sulfate, and the like.
Examples of the amine compound include triethylenediamine, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N '- (2-hydroxyethyl) -N, N, N' -trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N '-trimethyl-N' - (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) -N, N ', N ", N' -tetramethyl diethylenetriamine, N- (2-hydroxypropyl) -N, N '-tetramethyl diethylenetriamine, N, N' -trimethyl-N '- (2-hydroxyethyl) propanediamine, N-methyl-N' - (2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quininol, 3-quininol, 4-quininol, 1- (2 '-hydroxypropyl) imidazole, 1- (2' -hydroxypropyl) -2-methylimidazole, 1- (2 '-hydroxyethyl) imidazole, 1- (2' -hydroxyethyl) -2-methylimidazole, 1- (2 '-hydroxypropyl) -2-methylimidazole, 1- (3' -aminopropyl) imidazole, 1- (3 '-aminopropyl) -2-methylimidazole, 1- (3' -hydroxypropyl) imidazole, 1- (3 '-hydroxypropyl) -2-methylimidazole, N-dimethylaminopropyl-N' - (2-hydroxyethyl) amine, N-dimethylaminopropyl-N ', N' -bis (2-hydroxypropyl) amine, N-dimethylaminoethyl-N ', N' -bis (2-hydroxyethyl) amine, N-dimethylaminoethyl-N ', N' -bis (2-hydroxypropyl) amine, melamine, benzoguanamine, and the like.
Examples of the amine salt include amine salts of organic acid salts such as DBU (1, 8-diaza-bicyclo [5.4.0] undec-7-ene).
[ Filler ]
As fillers, known customary inorganic or organic fillers can be used, with particular preference being given to barium sulfate, spherical silica, titanium dioxide, norburg (Neuburg) silica particles and talc. In addition, aluminum hydroxide, magnesium hydroxide, boehmite, and the like may be used for the purpose of imparting flame retardancy. In addition, compounds having 1 or more ethylenically unsaturated groups or nano-silica (trade name) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names), nano-silica (trade name) XP 0516, XP 0525, XP 0314 (all product grade names) manufactured by Hanse-Chemie company, may also be used. They may be used alone or in combination of 2 or more. By including the filler, the physical strength and the like of the obtained cured product can be improved.
When the carboxyl group-containing resin is contained in the composition, the mixing amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass, per 100 parts by mass of the carboxyl group-containing resin in terms of solid content. When the mixing amount of the filler is 500 parts by mass or less, the viscosity of the photocurable and thermosetting resin composition does not become excessively high, the printability is good, and the cured product is hardly brittle.
[ photopolymerization initiator ]
In the present invention, as the photopolymerization initiator used for photopolymerization of the carboxyl group-containing photosensitive resin, a known photopolymerization initiator may be used, and among them, an oxime ester type photopolymerization initiator having an oxime ester group, an α -aminoacetophenone type photopolymerization initiator, and an acylphosphine oxide type photopolymerization initiator are preferable. The photopolymerization initiator may be used alone or in combination of 2 or more.
Examples of the oxime ester photopolymerization initiator include CGI-325 manufactured by BASF Japan, irgacure (registered trademark) OXE01, irgacure OXE02, N-1919 manufactured by ADEKA, inc., ADEKA Arkls (registered trademark) NCI-831, and the like.
In addition, a photopolymerization initiator having 2 oxime ester groups in the molecule can be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (III) can be given.
(wherein X is 1 Represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group (substituted with an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (substituted with an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), Y 1 Z represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group (substituted with an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (substituted with an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), an anthracenyl group, a pyridyl group, a benzofuryl group, a benzothienyl group, ar represents an alkylene group having 1 to 10 carbon atoms, an ethylene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, a thienyl group, an anthracenyl group, a thienyl group, a 2, 5-pyrrolediyl group, a 4,4 '-stilbene-diyl group, a 4,2' -styrenediyl group, and n represents an integer of 0 or 1. )
In particular, X in the above formula is preferred 1 、Y 1 Oxime ester photopolymerization initiators each of which is methyl or ethyl, Z is methyl or phenyl, n is 0, ar is phenylene, naphthylene, thienyl or thienyl.
As a preferable carbazole oxime ester compound, there may be mentioned a compound represented by the following general formula (IV).
(wherein R is 3 Represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms.
R 4 Represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms.
R 5 Can be linked by an oxygen atom or a sulfur atom, and represents an alkyl group having 1 to 20 carbon atoms which can be substituted by a phenyl group or a benzyl group which can be substituted by an alkoxy group having 1 to 4 carbon atoms.
R 6 Represents nitro, or X 2 -C (=o) -acyl.
X 2 An aryl group, a thienyl group, a morpholinyl group, a thiophenyl group, which may be substituted with an alkyl group having 1 to 4 carbon atoms, or a structure represented by the following formula (V). )
In addition, examples of the carbazole oxime ester compounds include those described in Japanese patent application laid-open No. 2004-359639, japanese patent application laid-open No. 2005-097141, japanese patent application laid-open No. 2005-220097, japanese patent application laid-open No. 2006-160634, japanese patent application laid-open No. 2008-094770, japanese patent application laid-open No. 2008-509967, japanese patent application laid-open No. 2009-040762, and Japanese patent application laid-open No. 2011-80036.
When the composition contains a carboxyl group-containing resin, the amount of the oxime ester-based photopolymerization initiator to be mixed is preferably 0.01 to 5 parts by mass per 100 parts by mass of the carboxyl group-containing resin in terms of solid content. When the content is 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating properties such as chemical resistance are improved. In addition, when the amount is 5 parts by mass or less, light absorption on the surface of the coating film tends to be suppressed, and deep curability tends to be improved. More preferably 0.5 to 3 parts by mass per 100 parts by mass of the carboxyl group-containing resin.
Specific examples of the α -aminoacetophenone photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, and N, N-dimethylaminoacetophenone. Examples of commercial products include Omnirad 907, omnirad 369, omnirad379, and the like manufactured by IGM Resins.
Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide, and bis (2, 6-dimethoxybenzoyl) -2, 4-trimethyl-pentylphosphine oxide. As commercial products, omnirad TPO, omnirad 819, manufactured by IGM Resins, etc. are mentioned.
Further, JMT-784 manufactured by Yueyang Kimoutain Sci-tech Co., ltd. Can be suitably used as the photopolymerization initiator.
When a photopolymerization initiator other than an oxime ester-based photopolymerization initiator is used, the amount of the photopolymerization initiator to be mixed is preferably 0.01 to 15 parts by mass per 100 parts by mass of the carboxyl group-containing resin in terms of solid content when the carboxyl group-containing resin is contained in the composition. When the amount is 0.01 parts by mass or more, the photocurability on copper is more reliable, and the coating properties such as chemical resistance are improved. In addition, when the amount is 15 parts by mass or less, a sufficient degassing reduction effect can be obtained, and further, light absorption on the surface of the cured coating film can be suppressed, and further, curability in a deep portion can be improved. More preferably 0.5 to 10 parts by mass per 100 parts by mass of the carboxyl group-containing resin.
A photoinitiating aid or sensitizer may be used in combination with the photopolymerization initiator. Examples of the photoinitiating auxiliary or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. These compounds may be used as photopolymerization initiators, but are preferably used in combination with photopolymerization initiators. In addition, the photoinitiating auxiliary or sensitizer may be used alone or in combination of two or more.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of the acetophenone compound include acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, and 1, 1-dichloroacetophenone. Examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone. Examples of the thioxanthone compound include 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, and 2, 4-diisopropylthioxanthone. Examples of the ketal compound include acetophenone dimethyl ketal and benzoin dimethyl ether. Examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4 ' -methyldiphenyl sulfide, 4-benzoyl-4 ' -ethyldiphenyl sulfide, and 4-benzoyl-4 ' -propyldiphenyl sulfide.
Examples of the tertiary amine compound include a compound having a dialkylaminobenzene structure such as an ethanolamine compound, a compound having a dialkylaminobenzene structure such as 4,4 '-dimethylaminobenzophenone (NISSOCURE (registered trademark) MABP manufactured by Seagaku corporation, japan), a dialkylaminobenzophenone such as 4,4' -diethylaminobenzophenone (EAB manufactured by Seagaku chemical Co., ltd.), a coumarin compound containing a dialkylamino such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), an EPA (Kayacure (registered trademark) manufactured by Japan chemical Co., ltd.), a Quantacure DMB manufactured by 2-dimethylaminobenzoic acid ethyl ester (International biosystem Inc.), a Quantacure BEA manufactured by 4-dimethylaminobenzoic acid isopentyl ester (International Biosynthetic Inc), and a Va (Va) manufactured by Dyacht chemical Co., ltd.) among commercial products. The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure, and among these, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450nm, and a coumarin ketone are particularly preferable.
As the dialkylaminobenzophenone compound, 4' -diethylaminobenzophenone is preferable because of low toxicity. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410nm and an ultraviolet region, and therefore is less colored, and it is possible to provide a colorless and transparent photosensitive resin composition, and it is possible to obtain a colored photosensitive film using a colored pigment and reflecting the color of the colored pigment itself. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable in view of exhibiting excellent sensitization to laser light having a wavelength of 400 to 410 nm.
Among these, thioxanthone compounds and tertiary amine compounds are preferable. In particular, by containing the thioxanthone compound, deep curability can be improved.
When the total amount of the photopolymerization initiator, the photoinitiating auxiliary agent, and the sensitizer is contained in the composition, the total amount is preferably 35 parts by mass or less per 100 parts by mass of the carboxyl group-containing resin in terms of solid content. When the amount is 35 parts by mass or less, light absorption is suppressed, and deep curability is also improved.
Since these photopolymerization initiator, photoinitiation auxiliary agent, and sensitizer absorb a specific wavelength, the sensitivity is lowered according to circumstances, and the photopolymerization initiator, photoinitiation auxiliary agent, and sensitizer may function as an ultraviolet absorber. However, these agents are not used solely for the purpose of increasing the sensitivity of the composition. The light with specific wavelength can be absorbed according to the requirement, the photoreactivity of the surface is improved, the line shape and the opening of the resist are changed into vertical, conical and reverse conical shapes, and the processing precision of the line width and the opening diameter is improved.
In addition to the above components, the photosensitive resin composition used in the photosensitive film of the present invention may contain other components such as a block copolymer, a colorant, an elastomer, and a thermoplastic resin. These components will also be described below.
The block copolymer may be suitably blended with the photosensitive resin composition. A block copolymer is a copolymer in which two or more polymers having different properties are covalently linked to form a long chain molecular structure. Preferably in the range of 20℃to 30 ℃. The catalyst may be solid in this range, or may be solid at a temperature outside this range. The photosensitive film is solid in the above temperature range, and is excellent in tackiness when it is formed or when it is coated on a support film and predried.
As the block copolymer, XYX or XYX' type block copolymers are preferred. Among the XYX or XYX' block copolymers, block copolymers composed of the following polymer units are preferred: the central Y is a soft block, the glass transition temperature Tg is low, preferably less than 0 ℃, and the two outer sides X or X' are hard blocks, the Tg is high, preferably more than 0 ℃. The glass transition temperature Tg is measured by Differential Scanning Calorimetry (DSC).
Among the XYX or XYX '-type block copolymers, a block copolymer comprising a polymer unit having a Tg of X or X' of 50 ℃ or higher and a polymer unit having a Tg of Y of-20 ℃ or lower is more preferable. Among the XYX or XYX 'type block copolymers, X or X' is preferably high in compatibility with the carboxyl group-containing resin, and Y is preferably low in compatibility with the carboxyl group-containing resin. Thus, it is considered that a specific structure is easily exhibited in a matrix by forming a block copolymer in which blocks at both ends are compatible with the matrix and a block at the center is not compatible with the matrix.
The block copolymer may be of the XYX or XYX' type, and may be used without any particular limitation as long as the hard block and soft block components are at least one type, respectively.
As the X or X' component, polymethyl methacrylate (PMMA), polystyrene (PS) and the like are preferable, and as the Y component, poly-n-butyl acrylate (PBA), polybutadiene (PB) and the like are preferable. In addition, a hydrophilic unit having excellent compatibility with the carboxyl group-containing resin, such as a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy unit, and an N-substituted acrylamide unit, is introduced into a part of the X or X' component, so that the compatibility can be further improved. The inventors of the present invention found that the block copolymer thus obtained has particularly good compatibility with the carboxyl group-containing resin, and surprisingly can improve cold and hot impact resistance, and further surprisingly, the elastomer-added substance has a tendency to decrease the glass transition temperature (Tg), whereas the block copolymer-added substance has a tendency not to decrease the Tg.
Examples of the method for producing the block copolymer include those described in Japanese patent application No. 2005-515281 and Japanese patent application No. 2007-516326. As a commercial product of the block copolymer, an acrylic triblock copolymer produced by living polymerization manufactured by Arkema company can be mentioned. Examples thereof include SBM type typified by polystyrene-polybutadiene-polymethyl methacrylate, MAM type typified by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, and MAM N type or MAMA type treated with carboxylic acid modification or hydrophilic group modification. Examples of the SBM type include E41, E40, E21, E20, etc., examples of the MAM type include M51, M52, M53, M22, etc., examples of the MAM N type include 52N and 22N, examples of the MAM a type include SM4032XM10, etc. Kuraritiy manufactured by KURARAY corporation is also a block copolymer induced by methyl methacrylate and butyl acrylate.
The block copolymer is preferably a 3-or more-membered block copolymer, and the block copolymer synthesized by living polymerization is more preferably a block copolymer in which the molecular structure is precisely controlled, from the viewpoint of obtaining the effect of the present invention. This is considered to be because the molecular weight distribution of the block copolymer synthesized by the living polymerization method is narrow, and the characteristics of each unit are clearly known. The molecular weight distribution of the block copolymer used is preferably 2.5 or less, more preferably 2.0 or less.
The weight average molecular weight of the block copolymer is usually preferably in the range of 20,000 ～ 400,000, more preferably 30,000 ～ 300,000. If the weight average molecular weight is less than 20,000, the targeted effect of toughness and flexibility is not obtained, and the tackiness is also poor. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity of the photocurable resin composition increases, and the printability and developability are remarkably deteriorated.
When the carboxyl group-containing resin is contained in the composition, the mixing amount of the block copolymer is preferably 1 to 50 parts by mass, more preferably 5 to 35 parts by mass, per 100 parts by mass of the carboxyl group-containing resin in terms of solid content. When the amount is 1 part by mass or more, the effect can be expected; when the content is 50 parts by mass or less, the photocurable resin composition exhibits excellent developability and coatability.
The photosensitive resin composition may contain a colorant. The colorant may be any of known colorants such as red, blue, green, and yellow, and may be any of pigments, dyes, and pigments. However, it is preferable that halogen is not contained in view of reducing environmental load and influence on human body.
Examples of the red colorant include monoazo-based, disazo-based, azo lake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, and quinacridone-based, and specifically include those having the following color index (c.i.; the Society of Dyers and Colourists publication) numbers.
Examples of the monoazo-based red colorant include pigment red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, and the like. Examples of the bisazo-based red colorant include pigment red 37, 38, 41, and the like. Further, as the monoazo lake-based red colorant, pigment red 48: 1. 48: 2. 48: 3. 48: 4. 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53: 1. 53: 2. 57: 1. 58: 4. 63: 1. 63: 2. 64: 1. 68, etc. Examples of the benzimidazolone-based red colorant include pigment red 171, 175, 176, 185, and 208. Examples of the perylene red colorant include solvent red 135, 179, pigment red 123, 149, 166, 178, 179, 190, 194, 224, and the like. Examples of the diketopyrrolopyrrole-based red colorant include pigment red 254, 255, 264, 270, 272, and the like. Examples of the condensed azo-based red colorant include pigment red 220, 144, 166, 214, 220, 221, 242, and the like. Examples of the anthraquinone-based red colorant include pigment red 168, 177, 216, solvent red 149, 150, 52, 207, and the like. Examples of the quinacridone-based red colorant include pigment red 122, 202, 206, 207, 209, and the like.
Examples of the blue colorant include phthalocyanine-based and anthraquinone-based pigments, which are classified into pigments (pigments), and examples thereof include Pigment blue 15 and Pigment blue 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60. As the dye system, solvent blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, and the like can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound may be used.
Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based, and examples of the anthraquinone-based yellow colorant include solvent yellow 163, pigment yellow 24, 108, 193, 147, 199, and 202. Examples of the isoindolinone yellow colorant include pigment yellow 110, 109, 139, 179, 185, and the like. Examples of the condensed azo yellow colorant include pigment yellow 93, 94, 95, 128, 155, 166, 180, and the like. Examples of the benzimidazolone-based yellow colorant include pigment yellow 120, 151, 154, 156, 175, 181, and the like. Examples of monoazo yellow colorants include pigment yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, and 62: 1. 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc. Examples of the disazo yellow colorant include pigment yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, and the like.
In addition to this, coloring agents such as violet, orange, brown, black, white, etc. may be added. Specifically, pigment black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, c.i. pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, pigment brown 23, 25, titanium dioxide, carbon black, and the like can be cited.
The mixing amount of the colorant is not particularly limited, and when the composition contains the carboxyl group-containing resin, the mixing amount is preferably 10 parts by mass or less, more preferably 0.1 to 7 parts by mass, per 100 parts by mass of the carboxyl group-containing resin in terms of solid content. The mixing amount of the white colorant such as titanium dioxide is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 3 to 80 parts by mass, per 100 parts by mass of the carboxyl group-containing resin in terms of solid content.
In addition, an elastomer may be blended in the photosensitive resin composition for the purpose of imparting flexibility to the obtained cured product, improving brittleness of the cured product, and the like. Examples of the elastomer include polyester-based elastomer, polyurethane-based elastomer, polyester urethane-based elastomer, polyamide-based elastomer, polyester amide-based elastomer, acrylic-based elastomer, and olefin-based elastomer. In addition, a resin obtained by modifying part or all of epoxy groups of epoxy resins having various backbones with a butadiene-acrylonitrile rubber modified with both terminal carboxylic acids may be used. Furthermore, an epoxy group-containing polybutadiene-based elastomer, an acrylic acid-containing polybutadiene-based elastomer, a hydroxyl group-containing isoprene-based elastomer, or the like can be used. The elastomer may be used alone or as a mixture of two or more.
In addition, for the purpose of improving the flexibility and touch dryness of the obtained cured product, a known and conventional adhesive polymer can be used. As the binder polymer, cellulose-based, polyester-based, and phenoxy resin-based polymers are preferable. Examples of the cellulose polymer include Cellulose Acetate Butyrate (CAB) and Cellulose Acetate Propionate (CAP) manufactured by Eastman corporation, and the polyester polymer is preferably Vylon series manufactured by eastern spinning corporation, and the phenoxy resin polymer is preferably a phenoxy resin of bisphenol a, bisphenol F, or hydrogenated compounds thereof.
When the carboxyl group-containing resin is contained in the composition, the mixing amount of the binder polymer is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass per 100 parts by mass of the carboxyl group-containing resin in terms of solid content. When the mixing amount of the binder polymer is 50 parts by mass or less, the alkali developability of the photosensitive resin composition is further improved, and the usable time for development becomes longer.
Further, the photosensitive resin composition may be further blended with an adhesion promoter, an antioxidant, an ultraviolet absorber, and the like, as necessary. They may use substances well known in the field of electronic materials. Further, at least one of known and customary thickeners such as fine silica, hydrotalcite, organobentonite and montmorillonite, at least one of defoamers such as silicone-based, fluorine-based and polymer-based and leveling agents, at least one of known and customary additives such as silane coupling agents such as imidazole-based, thiazole-based and triazole-based, rust inhibitors and fluorescent whitening agents may be blended.
The photosensitive film can be formed by coating the photosensitive resin composition on one surface of the support film and drying the same. In view of the coatability of the photosensitive resin composition, the photosensitive resin composition may be diluted with an organic solvent to adjust the viscosity to an appropriate level, and the coating may be performed with a uniform thickness on one surface of a support film by using a comma coater, a blade coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and the organic solvent may be volatilized by drying at a temperature of 50 to 130 ℃ for 1 to 30 minutes, whereby a non-tacky coating film may be obtained. The thickness of the coating film is not particularly limited, and is usually suitably selected in the range of 5 to 150. Mu.m, preferably 10 to 60. Mu.m, in terms of the film thickness after drying.
The usable organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, it is: ketones such as Methyl Ethyl Ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha and solvent naphtha. The organic solvent may be used alone or as a mixture of 2 or more kinds.
The evaporation and drying of the organic solvent may be performed using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection heating furnace, or the like (a method of bringing hot air in a dryer into convection contact using a device having a heat source of an air heating system using steam, or a method of spraying the hot air onto a support through a nozzle).
[ protective film ]
For the purpose of preventing dust or the like from adhering to the surface of the photosensitive film and improving the handleability, the photosensitive film laminate of the present invention may be provided with a protective film on the surface of the photosensitive film opposite to the intermediate layer.
As the protective film, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and a material having a smaller adhesion force between the protective film and the photosensitive resin layer than between the support film and the photosensitive resin layer is preferably selected. In addition, in order to facilitate peeling of the protective film when the photosensitive film laminate is used, the surface of the protective film, which is in contact with the photosensitive resin layer, may be subjected to the above-described release treatment.
The thickness of the protective film is not particularly limited, and is appropriately selected in the range of approximately 10 to 150 μm depending on the application.
< method for producing cured product and printed Circuit Board >
The photosensitive film or the photosensitive film laminate of the present invention is used to form a cured product. A method for forming the cured product and a method for manufacturing a printed wiring board including the cured product (cured coating) on a substrate on which a circuit pattern is formed will be described. As an example, a method of manufacturing a printed wiring board using a photosensitive film laminate having a protective film will be described. Firstly, i) peeling the protective film from the photosensitive film laminate to expose the photosensitive film; ii) bonding the photosensitive film of the photosensitive film laminate to the substrate on which the circuit pattern is formed; iii) Exposing the support film of the photosensitive film laminate to light; iv) removing the support film from the photosensitive film laminate and developing the support film to form a patterned photosensitive film on the substrate; v) curing the patterned photosensitive film by light irradiation or heat to form a cured coating film; thereby forming a printed circuit board. In the case of using a photosensitive film laminate without a protective film, the protective film peeling step (i step) is not necessarily required. Next, each step will be described.
First, the protective film is peeled from the photosensitive film laminate to expose the photosensitive resin layer, and the photosensitive resin layer of the photosensitive film laminate is bonded to the substrate on which the circuit pattern is formed. Examples of the circuit pattern-formed substrate include a copper-clad laminate using a paper-phenolic resin, a paper-epoxy resin, a glass cloth-epoxy resin, a glass-polyimide, a glass cloth/nonwoven fabric-epoxy resin, a glass cloth/paper-epoxy resin, a synthetic fiber-epoxy resin, a fluororesin, a polyethylene, a polyphenylene oxide, a cyanate ester, and the like, and a polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer sheet, and the like of all grades (FR-4, and the like) of materials such as a copper-clad laminate for a high-frequency circuit, in addition to a printed circuit board or a flexible printed circuit board, in which circuits are formed in advance.
In order to bond the photosensitive film of the photosensitive film laminate to the circuit board, it is preferable to bond the photosensitive film under pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, the photosensitive resin composition layer adheres to the circuit board, so that no air bubbles are mixed, and the hole filling property on the surface of the board is improved. The pressurizing condition is preferably about 0.1 to 2.0MPa, and the heating condition is preferably 40 to 120 ℃.
Then, exposure (irradiation of active energy rays) is performed from the support film of the photosensitive film laminate. By this step, only the exposed photosensitive resin layer is cured. The exposure step is not particularly limited, and for example, exposure may be selectively performed by passing active energy rays through a photomask having a desired pattern formed thereon by a contact type (or non-contact type) method, or the desired pattern may be exposed by the active energy rays by a direct drawing apparatus.
The exposure apparatus used for the active energy ray irradiation may be any apparatus that is equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, or the like and irradiates ultraviolet rays in the range of 350 to 450nm, or may be a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser beam using CAD data from a computer). The laser source of the direct imaging machine may be any of gas laser and solid laser as long as it is a laser having a maximum wavelength in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness, etc., and may be generally 20 to 800mJ/cm 2 Preferably 20 to 600mJ/cm 2 Within a range of (2).
After exposure, the support film and the intermediate layer are peeled off from the photosensitive film laminate and developed, thereby forming a patterned photosensitive film on the substrate. When the support film and the intermediate layer are peeled off, the surface of the photosensitive film cured by exposure is given the form of the intermediate layer surface. In the range of the non-destructive characteristics, the support film may be peeled off from the photosensitive film laminate before exposure, and the exposed photosensitive film may be exposed and developed.
The developing step is not particularly limited, and dipping, spraying, atomizing, brushing, and the like can be used. As the developer, an aqueous alkali solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like can be used.
Next, the patterned photosensitive film is cured by irradiation with active energy rays (light) or heat to form a cured product (cured coating film). This step is called main curing or additional curing, and can promote polymerization of an unreacted monomer in the photosensitive film, further thermally cure the carboxyl group-containing photosensitive resin and the epoxy resin, and reduce the amount of residual carboxyl groups.The irradiation with active energy rays may be performed in the same manner as the above-described exposure, and is preferably performed under conditions stronger than the irradiation energy at the time of exposure. For example, it may be 500 to 3000mJ/cm 2 . The heat curing may be performed under heating conditions at 100 to 200℃for about 20 to 90 minutes. The main curing is preferably performed after the photo-curing. By performing the photo-curing first, the flow of the resin can be suppressed even when the resin is cured by heating, and the molded surface can be maintained.
The photosensitive film laminate of the present invention can be suitably used for a printed wiring board, can be more suitably used for forming a solder resist layer, and particularly can be suitably used for forming a solder resist layer for IC packaging.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
< preparation of carboxyl-containing photosensitive resin >
A reaction vessel equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device was charged with 119.4g of a novolak-type cresol resin (Shonol CRG951, OH equivalent: 119.4, manufactured by Showa Denko Co., ltd.), 1.19g of potassium hydroxide, and 119.4g of toluene, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to a temperature. Then, 63.8g of propylene oxide is slowly added dropwise at 125-132 ℃ and 0-4.8 kg/cm 2 The reaction was carried out for 16 hours under the conditions. Then, the reaction solution was cooled to room temperature, 1.56g of 89% phosphoric acid was added and mixed to the reaction solution, and potassium hydroxide was neutralized to obtain a propylene oxide reaction solution of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2g/eq. The resulting novolak-type cresol resin had an average of 1.08 moles of alkylene oxide added per 1 equivalent of phenolic hydroxyl group.
293.0g of the obtained alkylene oxide reaction solution of novolak-type cresol resin, 43.2g of acrylic acid, 11.53g of methanesulfonic acid, 0.18g of methylhydroquinone and 252.9g of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air inlet pipe, air was introduced at a rate of 10 ml/min, and the mixture was reacted at 110℃for 12 hours under stirring. The water produced by the reaction distilled off 12.6g of water as an azeotropic mixture with toluene. After that, the reaction solution was cooled to room temperature, and 35.35g of the obtained reaction solution was neutralized with 15% aqueous sodium hydroxide solution, followed by washing with water. Then, 118.1g of toluene was distilled off while being replaced with diethylene glycol monoethyl ether acetate by an evaporator to obtain a novolak-type acrylic resin solution. Then, 332.5g of the obtained novolak type acrylic resin solution and 1.22g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air inlet pipe, air was introduced at a rate of 10 ml/min, 62.3g of tetrahydrophthalic anhydride was slowly added under stirring, and the mixture was reacted at 95 to 101℃for 6 hours to obtain a carboxyl group-containing photosensitive resin varnish 1 having an acid value of 88mgKOH/g and a nonvolatile content of 71%.
< preparation of photosensitive resin composition >
The carboxyl group-containing photosensitive resin varnish 1 obtained as described above, dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Japan chemical Co., ltd.), bisphenol a epoxy resin (epicolin 840-S manufactured by DIC corporation) and bisphenol novolac epoxy resin (NC-3000H manufactured by Japan chemical Co., ltd.), IRGACURE OXE02 manufactured by IGM Resins corporation or BASF Japan corporation as a photopolymerization initiator, barium sulfate (B-30 manufactured by samples chemical Co., ltd.) and/or spherical silica (Admafine SO-E2 manufactured by Admatechs corporation), melamine as a thermosetting catalyst, carbon black M-50 selected from the group consisting of triotsubishi chemical Co., ltd., dioxazine violet, c.i. pigment violet 23, c.i. pigment yellow 147, c.i. pigment blue 15 as a colorant were mixed with the photosensitive monomer dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Japan chemical Co., ltd.): each of 3 and c.i. pigment red 177 was mixed with diethylene glycol monoethyl ether acetate as an organic solvent in the proportions (parts by mass) shown in table 1, and the mixture was premixed by a mixer and kneaded by a three-roll mill to prepare photosensitive resin compositions 1 and 2.
< preparation of Melamine acrylic resin 1 >
The mass ratio is converted into 25 by solid components: 75, AMIDIR G-821-60 (isobutylated melamine resin, solid content 60%) manufactured by DIC Co., ltd.) and ACRYDIC A-405 (acrylic resin for melamine sintering, solid content 50%) manufactured by DIC Co., ltd were mixed, pre-stirred by a stirrer, and then kneaded by a three-roll mill to prepare melamine acrylate resin 1.
< preparation of epoxy Melamine resin 2 >
The mass ratio is converted into 25 by solid components: 75, a U-VAN 62 (isobutylated melamine resin, solid content 60%) manufactured by mitsubishi chemical corporation and an epomiik R301MIBK solution (bisphenol a type epoxy resin, solid content 60%) manufactured by mitsubishi chemical corporation were mixed, and pre-stirred by a stirrer, and then kneaded by a three-roll mill, thereby preparing an epoxy melamine resin 2.
< preparation of support film 1 having intermediate layer 1 >
The melamine acrylate resin 1 obtained as described above was diluted with methyl ethyl ketone to prepare a resin solution having a solid content concentration of 35 mass%. After methyl ethyl ketone was further added to the resin solution so as to achieve an appropriate solid content concentration depending on the thickness of the coating film, the mass ratio of each of the melamine acrylate resin 1, the silicone resin, and the silica having an average particle diameter of 2.3 μm was 59.7:0.3:40 (SYMAC US-270 manufactured by Toyama Synthesis Co., ltd.) and silica were added and stirred sufficiently at room temperature to obtain a uniform coating liquid. The coating liquid was applied to one surface of a polyethylene terephthalate film (Lumiror T60 manufactured by eastern corporation) as a support film by a gravure roll method, and dried at 130 ℃ for 20 seconds, thereby producing a support film 1 having an intermediate layer 1 (thickness of the intermediate layer 3 μm, thickness of the support film 25 μm, total thickness of 28 μm).
< preparation of support film 2 having intermediate layer 2 >
The support film 2 having the intermediate layer 2 (thickness of the intermediate layer 3 μm, thickness of the support film 25 μm, total thickness of 28 μm) was produced in the same manner as described above except that the epoxy melamine resin 2 obtained as described above was used instead of the acrylic melamine resin 1 in the production of the support film 1 having the intermediate layer 1.
TABLE 1
Example 1
< production of photosensitive film laminate >
To the photosensitive resin composition 1 obtained as described above, 300g of methyl ethyl ketone was added and diluted, and the mixture was stirred for 15 minutes by a stirrer to obtain a coating liquid. The coating liquid was applied to the surface of the support film 1 having the intermediate layer 1 on the intermediate layer side, and dried at 80℃for 15 minutes to form a photosensitive film having a thickness of 20. Mu.m. Next, a polypropylene film (OPP-FOA manufactured by Shineway chemical Co., ltd.) having a thickness of 18 μm was laminated on the photosensitive film to prepare a photosensitive film laminate.
< preparation of test substrate >
The surface of an FR-4 copper clad laminate (100 mm×150mm×0.8mmt, double-sided copper foil, copper foil thickness of 18 μm on both sides) on which a circuit was formed was subjected to chemical polishing using CZ8101 manufactured by MEC co, ltd, and the exposed surface of the photosensitive film exposed by peeling the polypropylene film from the photosensitive film laminate obtained as described above was bonded to the chemically polished surface of the substrate, followed by using a vacuum laminator (MVLP-500 manufactured by name machine) to press the resultant film to a degree of pressurization: 0.8Mpa, 70 ℃, 1 minute, vacuum: the test substrate 1 was produced by heat lamination under 133.3Pa to adhere the substrate to the photosensitive film.
Example 2
A test substrate 2 was produced in the same manner as in example 1, except that in example 1, the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.
Example 3
A test substrate 3 was produced in the same manner as in example 1 except that in example 1, a polyethylene terephthalate film 2 having an intermediate layer 2 was used instead of the support film 1 having the intermediate layer 1.
Example 4
A test substrate 4 was produced in the same manner as in example 3, except that in example 3, the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.
Comparative example 1
A test substrate 5 was produced in the same manner as in example 1 except that in example 1, a polyethylene terephthalate film (Lumiror T60 manufactured by ori corporation) having a thickness of 25 μm was used instead of the support film 1 having the intermediate layer 1.
Comparative example 2
A test substrate 6 was produced in the same manner as in comparative example 1, except that in comparative example 1, the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.
Comparative example 3
A test substrate 7 was produced in the same manner as in example 1, except that in example 1, a polyethylene terephthalate film (Lumiror T60 manufactured by ori corporation) having a thickness of 38 μm was used instead of the support film 1 having the intermediate layer 1.
Comparative example 4
A test substrate 8 was produced in the same manner as in comparative example 3, except that in comparative example 3, the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.
< resistance to falling of heavy object >
The test substrates of examples 1 to 4 and comparative examples 1 to 4, which were prepared as described above, were placed on concrete, and brass balls having a diameter of 30mm and a weight of 120g, which were weights, were dropped onto the surface of the polyethylene terephthalate film of each test substrate from the vertical direction at a height of 30 cm. Next, using a parallel light exposure apparatus equipped with a short arc type high pressure mercury lamp, physical exposure was performed from the polyethylene terephthalate film through an exposure mask, and then the polyethylene terephthalate film and the intermediate layer were peeled off to expose the photosensitive film. The exposure amount was 7-grid when exposure was performed from the polyethylene terephthalate film in contact with the photosensitive film using Stouffer41 grid. Pits generated by falling weights on the exposed surface of the photosensitive film were visually evaluated. The dropping of the weight was performed 10 for each test substrate of examples 1 to 4 and comparative examples 1 to 4. The evaluation criteria are as follows. Each test substrate was subjected to the test and evaluation 5 minutes after heat lamination in the above < preparation of test substrate >. The test and evaluation were carried out in a test environment at 23℃and a relative humidity of 50%.
O: pits were not observed on the surfaces of the 10 exposed photosensitive films.
X: pits were confirmed in 1 or more of the surfaces of 10 exposed photosensitive films.
The evaluation results are shown in table 2 below.
TABLE 2
As a method for easily confirming the impact resistance of the photosensitive film surface, a weight drop resistance test was performed and evaluated. As is clear from the examples, by using the photosensitive film laminate of the present invention, a photosensitive film laminate can be realized which does not affect the photosensitive film surface even by a strong impact when the laminated substrates and the like are overlapped. On the other hand, as is clear from the comparative example, the above-described effects cannot be achieved by using a photosensitive film laminate which does not satisfy the conditions of the present invention.

Claims (5)

1. A photosensitive film laminate comprising a support film, an intermediate layer, and a photosensitive film formed from a photosensitive resin composition in this order, characterized in that,
the intermediate layer comprises at least any one of melamine and melamine compounds,
the photosensitive resin composition comprises a carboxyl group-containing photosensitive resin and a thermal crosslinking component having at least 1 of 2 or more cyclic ether groups and 2 or more cyclic thioether groups in 1 molecule,
The intermediate layer is a layer in direct contact with the photosensitive film.
2. The photosensitive film laminate according to claim 1, wherein the support film has a thickness of 10 μm to 150 μm.
3. The photosensitive film laminate according to claim 1, wherein the photosensitive resin composition further comprises a filler.
4. The photosensitive film laminate according to claim 1, further comprising a protective film on a surface of the photosensitive film opposite to the intermediate layer.
5. A cured product formed by using the photosensitive film laminate according to any one of claims 1 to 4.
CN201810034826.8A 2017-01-17 2018-01-15 Photosensitive film laminate and cured product formed using same Active CN108333876B (en)

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JP2002131894A (en) * 2000-10-27 2002-05-09 Fuji Photo Film Co Ltd Plate making method for planographic printing plate without dampening water
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